Cellulose derivative compositions of matter and articles produced therefrom



'"pat enuao 'am o 2,216,8 7

. onttuiiosa teatime ooMr-osI'rIoNs 90F MATTERLAND ARTICLESMPRQDUCED rHnREFRoM it i James A. Mitchell, Kenmore, Y.,ias signor to i @E; I du Pontdevl {emours& Company, Wilmington, Del.,a corporation of Delaware, i

a in S erial No. 296,614 r t i t t. t t t 40JGlaims. (Cl'.t91---68) t t This invention relates to cellulose derivative lose derivative compositions and thatsuch plasticompositions and articles pro uced; therefrom; cizers are particularly usefuiin moistureproofing More particularly, this inventionrelates tomoiscompositions containing cellulose derivatives. t tureproofingcompositions and to the articiespro- Itis, therefore, an object of this invention to duced therefrom. a i provide anew ce11u1os'e derivative composition With the modern trends inthe development of containing, as a plastieizer, an arylarnide ofan the packaging of commodities, especially perish unsaturated aliphatic acid containing 3 to 24 carable foodstufistthe need h'as arisen for awrapping V bonatomsj i 2 t mat rial yvhichcan at once provide physical pro Another object of'this invention comprises the tection against contamination, preservation ac:- productionof a rnoistureproof film which fulfills tion by retaining within the package theoriginal the requirements for flexibility, transparency, and conditions, such as moisturecontent, and sales additionally possesses thefdesired surfacecharappeal b y; permitting examination of thepackage acteristics, such as a high degree of surface contentswithoutedestroyingtheyvrapper. These-1 smoothness, slip, and resistance to sticking under 15 needs have been lai gelyffiilfiiied by the recent storage conditions. t 1 introductionltdtheltrade ofawrapping material Further objects of the invention will appear comprising atransparent base sheet, such asre fro n'lthe following description and appended generated cellulose. coated with antransparent Claims. U v t y t t moistureproofing composition,,whichlatter may This'invention, in its preferred embodimenm is inone form thereof comprise a cellulose derive? primarily concerned with inoistureproofing com- 20 tive and a Iwax, with or without a resin ortblend positionsf'or the production of films either as a irig agent, and preferably also a plasticizer. t coating on a selected base, OIES'Q, self-sustaining These moistureproof vvrappintmateriais fare filn ycomprising a cellulose derivative, amoisit furnished to the consurner i in the" forrn ofcon-p tureproofing agent, a plasticizer, and preferably a tinuous jrollfstock "oias cut-tb-size sh etsnfln also aresinor other blending agent. The term. 25 y 1 ,ordenthatthe roll stocktwillifunroll sn' oothly pr fmoistureproofingfagent defines the material the cut-to-siz e sheetsfsparate easilyythe surface which serves as the basis for noistureproo fness.

of the material jrnust bes"rnoothand nontacky; In the forinulatio'n of cellulose derivative coating i t and there rnustbe notendency towards flaking-Oi compositions; it is well known in the art to use a! i i 3 sticking togethenduringgthe time ofstorage which plasticiz'ing agent to impart flexibilityto the'co'at intervenes bet veen manufacture"handmonsurribing This isaiso true inthe formulation of cellu- 1 tion. :rne moistureprooflngj composition, on-Lthe lose derivative 'coatingpompositions which conother hand, ustvibejtfieaible, transparent; and tain m'oistureproofine agents) but ithas been ob have good surfacecharacteristics. I i i i i servedthat the plasticizeralso contributes to the In my copendingapplication Seria1No.205,196, moistureproofing property, and, for'the produce filedApril 30, 1938, thereiis vdisclosedoceilulose tionf of highly moistureproof coating composiderivative compositions, and particularly jmois tionsgr'nore plasticizer is employed: than is necestureproofing cellulose derivative: compositions, sary merely for itspiasticizing action. The use I Containing as ai pl sfl t a on r i t ve of excess plasticizer to accomplish this function, of an arnidettofaf(saturated) fatty acid containe however; tends to impai'r the surface charaeteris- 4O ingl6jto IOcarbOn'atOms,andspe cifica1lyan;N+ ticsof the noistureproofingcoating compositions monophenyljderivativeoifan amide of a (satu since, withincreased plasticizer content, the comrated)Iattyaoidcontaining 6 to :10 carbonatoms position becomes softer and stickier; The soft In copending'application ofRohert BfFlintjsee" nessand stickiness arefobjectionable from the; rial 15103295250,flIed'ApriIZZO IQBBL there is gas point of view of giood surfacesiipand storage. =closed cellulose derivative eoinpositions, andpar-l 1 YEor the purposes ofthis invention, moisturet ticularly nioistureprooflng cellulosefderivative 5 proof materials are zdefined as those whiehgfin compositions, containing as a plasticizer a polytheffor'mpf a thin, continuousand unbroken sheet,

arylj derivative of an amide of a isaturated) fatty orfilrn, will perrnit the passage of not more than Y acid containnig'fi toYl8'carbon atorns,and"specif- 690grams of Water vapor per 100 square meters 9 ically an N-diphenylderivativeofanarnide-of a perhour'overa period of 24hours at approxi-v t I (saturated) fatty acidcontainin gi fito 18 carbon mate1y39.5 C.i0.5 C.,the relative humidity of i i atoms l have now foundfthajt aryl jamidespf the atmosphere at one side oi? the fllm being unsaturated aliphatic acids containing 3 ito 2 4 maintained at least at 98 and the relative huv a: oarbonfatonisflare adjective plasticizers fortce llu-f iniditv of the'atmosphereatthe other side being ini maintained at such value as to give a humidity differential of at least 95%.

Moistureproofing coating compositions are defined as those which, when laid down in the form of thin, continuous, unbroken films, applieduniiormly as a coating with a total coating thickness not exceeding 0.0005" to both sides of a sheet of regenerated cellulose of thickness approximately 0.0009", will produce a coated product which is moistureproof.

For the purposes of experimental tests, especially for those materials adaptable as coating compositions, moistureproof materials include those substances, compounds or compositions which, when laid down in the form'of a continuous, unbroken film applied uniformly as a coatin: with a total coating thickness not exceeding 0.10.25 C'.) with a water vapor differential of 5055 mm. (preferably 53.41037 mm.) of rnercury. For convenience, the number of grams of water vapor passed under these conditions may be referred to as permeability value". An un coated sheet of regenerated cellulose having a thickness of approximately 0.0009 will show a permeability value of the order of 6900.

, In the foregoing, it is apparent'that under the conditions set forth, a moistureprooied regen erated cellulose sheet is capable of resisting the passage of moisture or water vapor therethrough at least ten times as effectively as the uncoated regenerated cellulose sheet.

flhe'composition may be coated onto the base to givea wide range of coating thicknesses and, where heat sealingis desired, increase in the coating thickness will increase the heat sealing property of any given composition. For the purpose of this invention, and particularly where the ultimate coated sheet material is to be used as a wrapping tissue, the coating thickness is 0.00002" to 00005 and preferably 0.00005" on each side of the base.

In connection with this invention, it has been found that there are certain plasticizers for cellulose derivatives. especially in cellulose derivative inoistureproofing agent compositions, which are unique in their ability to plasticize and provide excellent surface. and storage characteristics. Though these plasticizers are not moistureproofing agents per. so. they tend in cellulose derivative moistureproofing agent coating compositions to increase lnoistureprooiness. The plasticizers which possess these unique properties are aryl mono or poly) amidesof unsaturated aliphatic acids containing 3 to 24 carbon atoms. The plasticizers of the instant invention may be used alone or in combination with other known plasticizers'to produce moistureproof films WhiCheXe I hibit a high degree of rnoistureproofness, good appearance, ilexibilty, transparency, excellent surfacc'slip, and storage without sticking or mar- '3 to 24 carbon atoms in combination with a cellulose derivative, '21 moistureproofing agent, and preferably a resin, or blending agent. In addition, other plasticizers. drying or non-drying oils,

additional resinous material of either the natural or synthetic varieties, coloring agents either as dyes or pigments, or other modifying agents may be used according to the type of coating compo sition desired. Obviously, for those uses where a transparent coated material is desired, any pigmerits or modifying agents which impair the transparency of the coating composition will be omitted therefrom. The proportions of the several ingredients may vary within rather wide limits depending on the properties desired in the finished composition, and these will be more specifically set forth below and will be illustrated in the several examples.

. As previously mentioned, the plasticizers contemplated by this invention are aryl (mono or poly) amides of unsaturated aliphatic acids containing 3 to 24 carbon atoms, which are not moistureproofing agents per se. Though various aryl derivatives of amides of unsaturated aliphatic acids containing 3 to 24 carbon atoms may be used, I have secured satisfactory results using N-substituted monoor diaryl amides of unsaturated aliphatic acids containing 3 to 24 carbon atoms. As illustrative examples of the plasticizers contemplated by this invention may be mentioned the N-substituted aryl amides prepared from mono basic unsaturated aliphatic acids containing 3 to 24 carbon atoms, such as produced from the following acids: acrylic, methyl-acrylic, dimethyl-acrylic,' crotonic, angelic, sorbic, oleic, linoleic, linolenic, erucic, ricinoleic, acetylated ricinoleic, clupanodonic, myristolenic, palmitolenic, eijaeostearic, undecylcnic, stearolic, (3-20 acids with 3 or 4 double bonds, and unsaturated acids derived from natural oils, such as cottonseed oil, corn oil, linseed oil, olive oil, rapeseed oil, sunflower oil, China-Wood oil, soya-bean oil, and marine oils, such as menhaden, porpoise, whale oil, etc.

As illustrative and referred species of the N- substituted monoaryl amides of unsaturated all phatic acids containing 3 to 24 carbon atoms may be mentioned the N-monophenyl derivatives of amides of said acids, and specifically monophenyl ricinoleamide, monophenyl oleamide, and

monophenyl (3-20 acid. As illustrative and preferred examples covering the N-substituted polyaryl amides of unsaturatedaliphatic acids con taining 3 to 24 carbon atoms may be mentioned the N-diphenyl derivatives of amides of said acids, and specifically diphenyl oleamide, diphenyl linoleamide, and diphenyl ricinoleamide.

The plasticizers may be prepared by reacting an aryl amine, such'as diphenyl airline or aniline, with the acid or the acid chloride under suitably controlled conditions or by other methods known in the art. Thus, materials which are capable of polymerization or oxidation may be used, if desired, after partial or complete oxidation or polymerization. Driers may be incorporated in the composition to insolubilize and harden it.

The plasticizers constituting the instant invention, particularly those obtained from the higher acids, are very effective in promoting moistureproofness in cellulose derivative moistureproofln'g compositions. They materially aid in producing films with good surface characteristics. Those plasticizers having drying properties may, after application of the composition containing the same, be cured to improve hardness, adhesion and anchorage.

As additional plasticizers for use in combination with those of this invention may be mentioned any of the known plasticizers, such as diamass? 6 zoic acid, such as butyl benzoyl benzoatederivaa Asblendingt agents, any ofthe' naturalor syntives of toluene sulfonamide; or the like 7 1 I thetic resinscommonly available may be used so Asmoistureprooflng agenta waxes or wax-like long as they are compatible 'and form homogeny-ymaterials such as paraffln, petrolatum, ceresin, eous .mixtures. "Such resins -may includeester 1 Japan waxjpalmuwax, beeswax, certain chlori gum,= rosinates, hydrogenated rosin, hydrogen- 10 ynated-hydrocarbons Chinese insect wax or other ated rosinesters, damm'anf copal; kauri, alkyd synthetic waxes" or waxi-like materials may be resins, vinyl derivatives, chlorinated dlphenyl used; If someiotj these waxes are too lsoft Iorthe resins; soluble resins ofthe phenol-formaldehyde H purposes desired; they maybe mixed with harder type. Non-resinousblendingagents may be used waxes or thegroup or with carnaubawanban when they yield homogeneous mixtures, and delillawwax, or other "harder" waxes Generally, these may include hydrogenated castor oil, castor mparafiiniservesas a satisfactorymoistureproofing oil phthalate; lanolin or wool grease, ethyl abieagent whichmaybe hardened if necessary by adtate, methyl abietate, diethylene glycol rosinate, mixture withcarnauba or candelilla wax. In the Rdiethylene glycol hydroros'ina'te, or the like. examples which accompany this specification; 1 As illustrative examples of moistureproofing paraflinhavinga melting pointof at least 60 C. coating compositions which embody thepr incihas beenemployed as typical of al highly satisfac ples of this invention, several specificeiramples, 1torymoistureproofingagent,"butvit is to beunthe proportions thereof being by weight, are derstoodnthat othermoistureproofing agents may hereinafter set forth, but they are not to be con- Wbesubstituted. I I s I 1 *"i 1 :sidered in any Wayjas limitative ofthe scope oi As thetcellulose derivative, there can beused ;this invention. M I l 1 Diphen ylcrotonamide Diphenyl linoleic-oleamidell Diphcnyllinolenamidm.

I Diplienyl ricinolearnidep- Monophcnyl ricinoleamidc.

- Diphenyl C-20 acid amid Monophcnylllinolenarnide.

Monophenylacrylamirlc.

1 Isobutyl acetate butyl phthalate, di-(methylcyclohexyly phthal ate, di-(dimethylcyclohexyl) phthalate,v methyl- Idimethylcyclohexyl) P adipate, dioycloheiryl adi pate, tricresyl phosphate; esters of o-benzoyl bento contribute towardsthe body and build of that composition in addition toxtheblending action. D'epending on the nature of the blending agent, more or less plasticizing action on the cellulose derivative may be obtained.

Diphcnyl erucaniideln I. Diphcnyl undecylenamida Monophcnyl undecylcnamidc Monophenyloleamidcll.

Monophcnyl 0-20 acid 1 amide! Paraffin: M. P. (10 C. Dewaxcd dajmrnar Hydrogenated ester Nitrocellulose lll4% N" Ethyl cellulose. L

S'olvent mixture Ethyl acetate .Q,... Toluene Ethyl 81001101.. Isobutyl alcohol.

Prepared from a mixture of 60% linoleic acid40%o1eic acid.

Preperedfrom unsaturated (l- 20 acids with 3 and 4 double bonds.

cellulose ethers, suchasglycol, ethyl, or benzyl cellulose; cellulose esters,such as cellulose nitratewhich; is particularly useful, cellulose acetate which is of limited compatibility; and such -mixed esters or ether-esters as cellulose acetatevnitrate, cellulose acetate-propionate or ethyl cellulose-nitrate. The cellulosejderivatives may be of various degrees of "conversion; as,j ior fexarnple, cellulose nitrates of various nitrogencontents.

7 p In the preparation of moistureproofing coating compositions comprising a cellulose derivative anda moistureproofing agent, it is advantageous to include some material whichimprove the compatibility-of these two ingredients. This ma- 1 terialisreferred to asva blending agent and is usually of a resinous na ture althoughthis is not I .ahsolutely"necessary; When the blending agent isresinous, advantage may be taken offits filmforming characteristics, it any," and slufiici'ent quantity may be added toa coating composition 'It is most 'convenientto apply the above moistureproofing coating compositions to base materials,-suc'h as sheets of regenerated cellulose, by means of suitable solvents. Thus, the film I forming ingredients; conveniently considered as solids, indicated in any of the above examples,

maybe dissolved .to give a coating composition of appropriate viscosity and solids content, whereupon thesolution may be applied to the desired baseiin accordance with the 'rnethods known in the art; solvents may be removed and the coated base subjected to an elevated temperature at least equal to the melting point of the wax, whence; "after cooling, a clear, transparent, flexible; moistureproof, coatedbase having good surface ychjaracteristicsi willbe obtained. A suitable technique for this operation is set forth in the "Qharchtz Prindle Patent No. 1,737,187. 3 7 y The table hereinbefore set forth contains solvent compositions used in connection with the coating compositions of the examples. The solvent mixtures maybe modified by the addition of the properties of the plasticizers as set forth in this specification.

These moistureproofing compositions may be applied to various sheet materials to produce wrapping tissues which are flexible, moistureproof, and which exhibit highly 'improyed surface characteristics including excellent surface slip and resistance to caking, sticking or marring during storage. .A- variety of base sheet materials may be used, such as cellulosic materials, paper, albuminous materials. (gelatin, agaragar, casein), or films made from rubber derivatives, e. g., rubber "hydrochloride, chlorinated rubber, or the material preparedby reacting rubber and a metal halide, such as boron trifluoride, stannous or stannic chloride, stannic acid, and

other materials which are disclosed inan article by Thies and Clifford, in the Journal of Industrial and Engineering Chemistry, vol. 26, page 123 (1934), ,themethod of. reacting the materials conforming to that disclosed in the said article referred to. .In the preferred embodiment of the invention, a non-porous, non-fibrous,

dense, smooth-surfaced and preferably transparent material, such as regenerated cellulose, cellulose ester films including cellulose nitrate and cellulose acetate, or cellulose ether films including ethyl cellulose, benzyl cellulose, glycol cellulose or lowly etherified cellulose, such as those in which there is only one substituent group for several glucose units of cellulose, is employed.

In the coating compositions set forth 'in the above examples, it is apparent that the proportions of the several ingredients may bevaried overa considerable range. Thus, the cellulose derivative ,may comprise 30%'70% or more of the total solids, although in most instances 50%-70% will be found satisfactory, with approximately 60% a convenient and generally useful prop'ortion.- The ratio of cellulose derivative to blending agent may vary over a Wide range from 2:1 to 10:1, or even greater, but for most purposes a ratio of from 3:1 to 9:1 is satisfactory, while a ratio of 4:1 is convenient and yields generally good results. The cellulose derivative is usually in excessof the total plasticizer content, and the ratio of cellulose derivative to plasticizer mayvary from 1:1 to 6:1, but a ratio of 1-1 /2:1 to-4:1'is generally found to give the best results.

The blending agent may vary according to the cellulose derivative, plasticizer or moistureproofing agent employed, and it may constitute 1%-20,% or more of the total solids. The ratio of blending agent to moistureproofing agent may vary from 1:5 or less to 5:1 or more, and usually a ratio of approximately 3:1 or 4:1 will befound satisfactory. The larger amounts of blending agent are usually used when the blending agent exerts some plasticizing action and can therefore replace a portion of the plasticizer.

The moistureproofing agent is usually present in a quantity sufficient to impart a suitable degree of moistureproofness while still maintaining homogeneity of composition, so that the ultimate moistureproofing coating on the moistureproof article prepared in accordance with the invention will be clear, transparent, non-greasy, non,- smeary, and non-tacky under the normal conditions of handling or storage. Generally speaking, if the moistureproofing agent constitutes less described in the examples.

than 10% of the total solids, these conditions will be fulfilled, but while 2%-6% ofmoistureproofing agent has'been found to yield excellent results, it is to be understood that more or less may be used depending on the nature of the moistureproofing agent or the degree of moistureproofness desired.

The plasticizer may consist of an N-aryl (mono or poly) amide of an unsaturated aliphatic acid of the type previously mentioned or a mixture of plasticizers containing appreciable quantities of one or more specific compounds hereinbefore mentioned. The total plasticizer concentration may vary from 10%-60% ofthe total solids. Low percentages of plasticizer, however, are usually used only when the blending agent is'capable of exhibiting a plasticizing action andtherefore substitutes for a portion of plasticizer which mightotherwise be added.

In the preceding discussion of the proportions of ingredients in the coating compositions, the ranges of percentage composition or ratio have been given to facilitate the formulation of highly satisfactory and preferred compositions and to aid one skilled in the art in quickly and easily arriving at operable compositions not specifically It is furthermore, however, to be understood that these limiting ranges are largely illustrative and do not restrict the invention beyond the limitations set forth in the appended claims.

Though the invention in its preferred embodiment relates to moistureproofing compositions and articles produced therefrom, the invention is not'restricted thereto. The plasticizers may be used in cellulose derivative compositions for producing protective coatings and also in the production of cellulose derivative plastic or molding compositions. In the production of protective coatings (non-moistureproof coatings) the plasticizer may vary between 10%-75% of the total solids, but the range of 13 %-30% will be generally satisfactory. In the case of plastics, the concentration'of the plasticizer may vary from 10%- 50% of the composition, or even greater, depending upon the cellulose derivative. The following examples illustrate the use of these plasticizers in protective coatings:

The following examples illustrate plastic or molding compositions:

Example 3 Parts by weight Cellulose acetate Diphenyl C20 acid amid'e 40 Example 4 7 Parts by weight Cellulose nitrate 100 Diphenyl linoleamide 60 lose derivative and as 'la plasticizer, awmonoaryl amide of an unsaturated aliphatic acid contain Ethyl, cellulose Monophenyl; ricinoleamlde e 3 5 ,Sinceitjis obvious that various changes and modifications may bemadein the a bove descrip tion without departing from the nature or spirit thereofythis invention is not restricted thereto except as set forthin the appended claims. a

1': F A- composition of matter comprising a cellu-1 losederivative andas a plasticizer an aryl amide of an unsaturated"aliphatici acid containing3 to v 2.4 carbon atoms", said pjlasticizer being per se nonmoistureproofing, and said a cellulose derivative being selectedirorn the classwhich consistsof cellulose esters,

0811111656 ethers cellulose ether-esters.- l

2. A composition of matter comprising a celluing 3 to 2 4 carbonatomssaid plasticizer being derivative being selected from the class which con sists of cellulose esters, cellulose ethersand cellu lose ether-esters.

3. A composition oi? matter comprising a cellulose derivative and'fasa plasticizer, a polyaryl y amide of, an unsaturated aliphatic acid containing 3=to 24 carbon atoms; saidplasticizer being per se non-moistureprooflng, and'said cellulose V derivative beingselected from the class which consists ofcellulose esters, cellulose ethers and cellulose ether-esterswl i l 4; A composition ofjmajtter comprising a cellulose derivative and asa plasticizer an N- substituted arylamide' of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per senon-moistureproofing, and said cellulose derivativebeing selected from the class which consists of cellulose esters, cellulose ethersand cellulose ether-esters.

5; .A- composition of matter comprising a cellu lose derivative and as .a plasticizer an f N-substi tutedfmonoaryl amide of an unsaturated aliphatic acid containing 3to 24 carbon atoms, said plasticizer being per se non-moistureproofing, and said cellulose derivative being selectedfrom the class ,WhiOhTcOl'lsiStS of cellulose esters, cellu loseethersand cellulose ether-estersp 6. A composition of matter comprisingraicellu lose derivative and 3.518. plasticizen an'N-substh tuted diarylwamide of, an unsaturated aliphatic acid containing 3tog24 carbonatoms, saidplasticizer being per se non moistureprooflng, and i said cellulose derivative being selected from the class which consists of cellulosewesters, cellulose ethers and cellulose: ether esters. i i

, ,7. A composition of mattercomprislng a cellulose derivative and asa plasticizeran N-phenyl derivative of an amide of: an unsaturated all- 1 ,phaticaacid containing3 to 24 carbonatoms, said plasticizer being per se non-molstureprooflng, and said 1 cellulose derivative; being selected; from the classxwhich' consists of cellulose esters, cellu-- lose ethers andcellulose ether-esters. I

*8. Acomposition of matter comprising a cellu lose derivative and as a plasticizer an N-monophenyl derivative of an amideof an unsaturated aliphatic acid containing 3 to24-,carbon atoms,

said plasticizer being per se non-moisturepx'oofl ing, and saidcellulose derivative being selected from the class which consists of cellulose esters, 7

cellulose ethers and celluloseether-esters;

v c 9, A composition of acid containing 3- to 24 carbon atoms, said piesticizer being: per sefnon-moistureproofin a and said cellulose derivative beinglselected fromwthe" class .which consists-o1 cellulose esters, cellulose ethersiand cellulose ether-esters." i a 10. A" composition of matter comprising a cellulose derivativeand as a plasticizer diphenyl oleamide; said cellulose derivative being selected i'romithe class which consists of cellulose esters, cellulose ethers and cellulose ether-esters. 1

11; A composition of matter comprising [a cellulose derivativeand as a plasticizer monophenyl oleamide, said-cellulose derivative being selected mm thejclass whichconsists 0t cellulose esters, cellulose ethers and cellulose ether-esters. 12; composition of matter, comprising i a cellulosederivative and as a plasticizer diphenyl j linoleamide," said cellulose derivative being selected from the class whichconsists of cellulose esters, cellulose ethers and cellulose ether-esters. 13.A film-forming composition comprising a cellulose rderivative, a moistureproofing agent,

andas-a plasticizer an N-substituted aryl amide of an unsaturatedtaliphaticacid containing 3 to 24 carbon atomsssaid plasticizerlbelng per .se

non moistureprooflng, and said cellulose derivativebeing selected from the class which consists v tter. comprising a cellulose derivativeand as a plasticizer an N-diphenyl derivative of an amide of an unsaturated aliphatic of cellulose esters, cellulose ethers and cellulose ether-esters. i i

-14.,-A film-forming composition comprising a cellulose derivative, a ,moistureproofing agent, and as a plasticizer an ,N substittited monoaryl amide of an unsaturatedaliphatic acid containing 3 to 2 carbon atoms, said plasticizer being per se non-moistureproofing, and said! cellulose derivativebeing selected froxnthe class which consists of cellulose esters, cellulose ethers and cellulose ether-esters.

15. A film-forming composition comprising a cellulose derivative, a moistureproofing agent,

and asQa plasticizer an N-substituted diaryl y amide of'an unsaturated aliphatic acid containing 3l t024 carbon atoms, said plasticizer being per senon-moistureproofing, and said cellulose derivative'being selected from the class which consists oi cellulose esters, cellulose ethers and cellulose ether-esters} v v l6.A film-forming composition comprising a cellulose derivative, a moistureprooflng agent,

and as a plasticizeranN-phenyl derivative of an amide of an unsaturatedaliphaticacid containing 3 to 2 4 carbon atoms, said plasticizer being per se non-moistureprooflng, and said cellulose derivativebeing selected from the class which consists of cellulose esters; cellulose ethers an cellulose ether-esters.

17. A film-forming composition comprising-a cellulose derivative, a moistureproofing agent, andasa plasticizer an N-monophenyl derivative of anfamide of an unsaturated aliphaticYa cid containing3 to 24 carbonatoms, said plasticizer being per ,se non moistureprooflng, and said cellulose derivative being selected "from the class which consistsof cellulose esters,cel1ulose ethers and cellulose ether-esters.

18; A"f1lm-forming composition comprising a cellulose I derivative, a moistureproofing agent,

and as a plasticizerian N-diphenyl derivativeot anamide oflan unsaturated aliphatic acid containing'li to. 24 carbon atoms, said plastlcizer being." per" se non-moistureprooflng, and said i cellulose derivative being selected fromthe class which consists of. cellulose esters, cellulose ethers and cellulose ether-esters.

-19.A.' film-forming composition comprising a cellulose derivative, a moistureproofing agent, a

blending agent, and as a plasticizer an N -substi-,

tuted aryl amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se non-moistureproofing, and said cellulose derivative being selected from. the class whichconsists of cellulose esters, cellulose ethers and cellulose ether-esters, the ratio of the quan-v tity of cellulose derivative to the quantity of blending agent being from 2:1 to 10:1.

20. A film-forming composition comprising a cellulose derivative, a moistureproofing agent, a blending agent, and as a plasticizer an N-substituted arylamide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se non-moistureproofing; and said cellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers and cellulose ether-esters, the ratio of the quantity of cellulose derivative to the quantity of plasticizer being from 1:1 to 6:1.

21. A film-forming composition comprising a cellulose derivative, a moistureproofing agent, a blending agent, and as a plasticizer an N-substituted aryl amide of an unsaturated aliphatic acid con'taining3 to 24 carbon atoms, said plasticizer being per se non-moistureproofing, and said cellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers and cellulose ether-esters, the ratio of the quantity of blending agent to the quantity of moistureproofing agent being from 1:5 to 5:1.

22. A film-forming composition in which the solids comprise the following ingredients in approximately the following proportions, the proportions being by weight and based on the total solids content:

Per cent Cellulose derivative 30 to '70 Plasticizer 10 to 60 Blending agent -l.- to 20 Moistureproofing agent Not over 10 the plasticizer comprising an aryl amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se nonmoistureproofing, and said cellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers and cellulose ether-esters.

23. An article of manufacture comprising a base coated with a composition comprising a cellulose derivative and as a plasticizer an N- substituted aryl derivative of an amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se nonmoistureproofing, and said cellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers and cellulose ether-esters.

24. An article of manufacture comprising a cellulose derivative and as a plasticizer an N- substituted polyaryl derivative of an amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se nonmoistureproofing, and said cellulose derivative being selected fromthe class which consists of cellulose esters, cellulose ethers and cellulose ether-esters.

26. An article of manufacture comprising a base coated with a composition comprising a cellulose derivative and as a plasticizer an N- phenyl derivative of an amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se non-moistureproofing, and said cellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers and cellulose ether-esters.

27. An article of, manufacture comprising a base coated with a composition comprising a cellulose derivative and as a plasticizer an N- monophenyl derivative of an amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se nonmoistureproofing, and said cellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers and cellulose ether-esters.

28. An article of manufacture comprising a base coated with a composition comprising a cellulose derivative and as a plasticizer an N- diphenyl derivative of an amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se non-moistureproofing, and said cellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers and cellulose etheresters.

29. An article of manufacture comprising a base sheet formed of a transparent, non-fibrous material coated with a transparent moistureproofing composition comprising a cellulose derivative, a moistureproofing agent and as a plasticizer an N-substituted aryl derivative of an amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se non-moistureproofing, and said cellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers and cellulose ether-esters.

30. An article of manufacture comprising a base sheet formed of a transparent, non-fibrous material coated with a transparent moistureproofing composition comprising a. cellulose derivative, a moistureproofing agent and as a plasticizer an N-substltuted monoaryl derivative of an amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se non-moistureproofing, and said cellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers and cellulose ether-esters.

31. An article of manufacture comprising a base sheet formed of a transparent, non-fibrous material coated with a transparent moistureproofing composition comprising a cellulose derivative, a moistureproofing agent and as a plasticizer an N-substituted polyaryl derivative of an amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se non-moistureproofing, and said cellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers and cellulose ether-esters.

32. An article of manufacture comprising a base sheet formed of a transparent, non-fibrous moistureprooflng, and said cellulose derivative being selectedfrom the class which consists of of an unsaturated aliphatic acid containing 3 to materlalcoated with a transparent moistureprooflng composition comprising a cellulose del rivative, a moistureprooflng agent and as aplasticizer an N-phenyl derivative of an amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizer being per se noncellulose esters, cellulose ethers and cellulose ether-esters.

33. An article of manufacture comprising a base sheet formed of a transparent, non-fibrous material coated with a. transparent moistureproofing composition comprising a cellulose derivative, a moistureprooflng agent and as a plasticlzer an N-monophenyl derivative of an amide 24 carbonatoms, said plasticizer being per se non-moistureproofing, and saidflcellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers andcellulose ether-esters. i I 34. An article of manufacture comprising a base sheet formed .of'a transparent, non-fibrous material coated withfa transparent moistureproofing composition comprising a cellulose de-- rivative, a moistureprooflng agent: and as a plasticizer an N-diphenyl derivative of an amide of an unsaturated aliphatic acid containing 3 to 24 carbon atoms, said plasticizerbeing per se nonmolstureprooilng, and said cellulose derivative beingv selected from the class which consists of cellulose it esters, cellulose ethers and cellulose ether-esters: i v 35., An article of manufacture comprising i a base coated with a composition comprising a cellulose derivative and as aplasticizer ,diphenyl oleamide, said cellulose derivative-being selected from the class-which consists of cellulose esters, cellulose ethers and cellulose ether-esters.

36. An article of, n anufacturecomprising a base coated with a composition comprising a cellulose derivative and as a plasticizer mono phenyl oleamide, saidcellul ose derlvativebeing forth, the proportions being by weight:

selected from the class which consists of cellulose esters, cellulose ethers and cellulose ether-esters. 37. An article of manufacture comprising a base coated with a composition comprising a cellulose derivative and as a plasticizer diphenyl linoleamide, said cellulose derivative being selected from the class which consists of cellulose esters, cellulose ethers and cellulose ether-esters.

38; An article of manufacture comprising a base sheet formed of atransparent, non-fibrous material coated with a transparent, moistureproofing composition comprising the following ingredients in the approximate proportions set 39. article of manufacture comprising a base sheet formed of a transparent, non-fibrous 40. An article of nianufacture comprising a base sheet formed of atransparent, non-fibrousmaterial coated with a transparent, moistureprooflng composition comprising the following ingredients in the approximate proportions set forth, the proportions being by weight:

, Per cent Nitrocellulose (12.5% N) 63 Dewaxed dammar 15 Paraflln (M. P. 60 C.) 4

; Monophenyl oleamide 18 Jar/ms A. MITCHEIL.

, Per cent Nitrocellulose (12.5% N) 5'7 Ester gum l5 rammn (M. PL 60 C.) 4 Diphenyl ol eamide 24 material coated, with a transparent, moisture: proofing composition comprising the following ingredientsrin' the approximate proportions set 

